EP1657775A1

EP1657775A1 - Electrolyte for lithium battery and lithium battery comprising same

Info

Publication number: EP1657775A1
Application number: EP05110102A
Authority: EP
Inventors: Dae-Yup Shin; Dong-Hyun Jung; Soo-Jin Park; Kyoung-Han Yew; Hyun-Jeong Lim
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2004-11-03
Filing date: 2005-10-28
Publication date: 2006-05-17
Anticipated expiration: 2025-10-28
Also published as: EP1657775B1; KR20060039568A; DE602005012774D1; JP2006134885A; US7438993B2; KR100628470B1; US20060127776A1; JP4842617B2

Abstract

The electrolyte for a lithium battery includes a non-aqueous organic solvent, a lithium salt, and an additive of the following Formula 1:

wherein, X and Y are the same or different from each other and selected from O, S, CR₂, or NR, where here R is H, a halogen, or an alkyl having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and both X and Y are not oxygen (O),
R_a to R_d are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R_a to R_d is a halogen.

Description

FIELD OF THE INVENTION

The present invention relates to an electrolyte for a lithium battery, and a lithium battery comprising the same, and more particularly, to an electrolyte for a lithium battery which inhibits overcharging of the battery, and a lithium battery comprising the same.

BACKGROUND OF THE INVENTION

The use of portable electronic instruments is increasing as electronic equipment gets smaller and lighter due to developments in high-tech electronic industries.
Studies on lithium secondary batteries are actively being pursued in accordance with the increased need for a battery having high energy density for use as a power source in these portable electronic instruments. Such a lithium secondary battery, having an average discharge potential of 3.7V (i.e., a battery having substantially a 4V average discharge potential) is considered to be an essential element in the digital generation since it is an indispensable energy source for portable digital devices such as cellular telephones, notebook computers, camcorders, etc. (i.e., the "3C" devices).
Also, there has been extensive research on batteries with effective safety characteristics such as preventing overcharging.
When a battery is overcharged, an excess of lithium ions is deposited on a positive electrode, and an excess of lithium ions is also inserted into a negative electrode, making the positive and negative electrodes thermally unstable. An eruptive explosion occurs from a decomposition of the electrolytic organic solvent, and the thermal runaway that occurs causes serious problems of battery safety.
To overcome the above problems, it has been suggested that an aromatic compound such as an oxidation-reduction additive agent ("redox shuttle") be added to the electrolyte. For example, U.S. Patent No. 5,709,968 discloses a non-aqueous lithium ion secondary battery to prevent thermal runaway resulting from an overcharge current by using a benzene compound such as 2,4-difluoroanisole. U.S. Patent No. 5,879,834 discloses a method for improving battery safety by using a small amount of an aromatic compound, such as biphenyl, 3-chlorothiophene, furan, etc., which is electrochemically polymerized to increase the internal resistance of a battery during unusual overvoltage conditions. Such redox shuttle additives increase the temperature inside the battery early due to heat produced by the oxidation-reduction reaction, and close pores of a separator through quick and uniform fusion of the separator to inhibit an overcharge reaction. The polymerization reaction of these redox shuttle additives consumes the overcharge current to improve battery safety.
However, the need for high capacity batteries is increasing, and these redox shuttle additives cannot provide the high level of safety required of such high capacity batteries. Therefore, a need exists for an electrolyte capable of preventing overcharge and ensuring battery safety.

SUMMARY OF THE INVENTION

An exemplary embodiment of the present invention provides an electrolyte for a lithium battery capable of improving battery safety.
Another embodiment of the present invention provides a lithium battery which includes the above electrolyte.
According to one embodiment of the present invention, an electrolyte for a lithium battery includes a non-aqueous organic solvent, a lithium salt, and an additive. The additive is represented by the following Formula 1:
wherein, X and Y are the same or different from each other and selected from O, S, CR₂, or NR, where here R is H, a halogen, or an alkyl having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and both X and Y are not oxygen (O),
R_a to R_d are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R_a to R_d is a halogen.
According to another embodiment of the present invention, a lithium battery is provided, which includes the above electrolyte, a positive electrode including a positive active material being capable of intercalating and deintercalating lithium ions, and a negative electrode including an active material selected from the group consisting of a material being capable of intercalating/deintercalating lithium ions, a lithium metal, a lithium-containing alloy, and a material being capable of forming a lithium-containing compound by reversibly reacting lithium.

BRIEF DESCRIPTION OF THE DRAWING

The accompanying drawing, which is incorporated in and constitutes a part of the specification, illustrates embodiments of the invention, and together with the description, serves to explain the principles of the invention.
FIG. 1 is a cross-sectional view of a non-aqueous lithium battery cell.

DETAILED DESCRIPTION OF THE INVENTION

In the following detailed description, embodiments of the invention have been shown and described, simply by way of illustration of the best mode contemplated by the inventors of carrying out the invention. As will be realized, the invention is capable of modification in various respects, all without departing from the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not restrictive.
A cross-sectional view of a general non-aqueous Li-ion cell is shown in FIG. 1.
The Li-ion cell 1 is fabricated by inserting an electrode assembly 8 including a positive electrode 2, a negative electrode 4, and a separator 6 interposed between the positive and negative electrodes 2 and 4 into a battery case 10. An electrolyte 26 is injected into the battery case 10 and impregnated into the separator 6. The upper part of the case 10 is sealed with a cap plate 12 and a sealing gasket 14. The cap plate 12 has a safety vent 16 to release pressure. A positive electrode tab 18 and a negative electrode tab 20 are respectively attached on the positive electrode 2 and the negative electrode 4. Insulators 22 and 24 are installed on the side and lower parts of the electrode assembly 8 to prevent a short circuit occurrence in the battery.
In a lithium battery, the temperature of the battery increases abruptly because of overcharging due to incorrect operation or break-down of the battery, or a short circuit occurrence due to a defect in the battery design, so that thermal runaway takes place. During overcharging, an excessive amount of lithium ions are released from the positive electrode and deposited on the surface of the negative electrode to render the positive and negative electrodes unstable. As a result, exothermic reactions such as pyrolysis of an electrolyte, reactions between the electrolyte and lithium, an oxidation reaction of the electrolyte on the positive electrode, a reaction between the electrolyte and oxygen gas that is generated from the pyrolysis of the positive active material, etc., rapidly increase the temperature inside the battery to cause thermal runaway, and thus, the generation of fire and smoke.
In order to address the above problems, in the present invention a compound represented by the following Formula 1 is used as an electrolyte additive to improve battery safety on overcharging:
wherein, X and Y are the same or different from each other and selected from O, S, CR₂, or NR, where here R is H, a halogen, or an alkyl having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and both X and Y are not oxygen (O),
R_a to R_d are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R_a to R_d is a halogen.
One preferred example of the additive compound is represented by the following Formula 2:
wherein, R¹ and R² are the same as R in the definition of Y₁, and R³ to R⁶ are the same as R_a to R_d in the above Formula 1. That is to say, R³ to R⁶ are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and at least one of R³ to R⁶ is a halogen.
Another preferred example of the additive compound is a compound represented by the following Formula 3 where in the above Formula 1, X is O, and Y is CH₂:
wherein, R_a to R_d are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and at least one of R_a to R_d is a halogen.
Another exemplary compound is represented by the Formula 4:
wherein, R¹ and R² are the same as R in the definition of X, R³ and R⁴ are the same as R in the definition of Y, and R⁵ to R⁸ are the same as R_a to R_d in the above Formula 1. That is to say, R⁵ to R⁸ are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and at least one of R⁵ to R⁸ is a halogen.
Another exemplary compound is represented by the Formula 5:
wherein, R_a to R_d are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and at least one of R_a to R_d is a halogen.
Another exemplary compound is represented by the Formulas 6 to 15.
The additive compound represented by the above Formula 1 initiates polymerization at more than about 4.5V to coat an electrode surface and increase resistance between positive and negative electrodes. Alternatively, the compound performs an oxidation/reduction reaction at a voltage of more than about 4.5V to consume an applied current at overcharge and ensure safety of a lithium battery.
The additive compound of the above Formula 1 may be used in an amount of 0.01 to 50wt%, preferably 0.01 to 30wt%, more preferably 0.01 to 10wt%, and still more preferably 0.01 to 5wt%, based on the total weight of the electrolyte. When the amount of the compound is less than 0.1wt%, the electrolyte may be ignited. When it is more than 50wt%, a battery performance may be deteriorated.
The additive compound is added to a non-aqueous organic solvent including a lithium salt. The lithium salt acts as a supply source of lithium ions in the battery, making the basic operation of a lithium battery possible. The non-aqueous organic solvent plays a role of a medium wherein ions capable of participating in the electrochemical reaction are mobilized.
The lithium salt is preferably at least one selected from the group consisting of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃, Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiAlO₄, LiAlCl₄, LiN(C_xF_2x+1SO₂)(C_yF_2y+1SO₂) (wherein x and y are natural numbers), LiCl, Lil, and a mixture thereof.
The concentration of the lithium salt preferably ranges from 0.6 to 2.0M, more preferably 0.7 to 1.6M. When the concentration of the lithium salt is less than 0.6M, the electrolyte performance deteriorates due to its ionic conductivity and when the concentration of the lithium salt is greater than 2.0M, the lithium ion mobility decreases due to an increase of the electrolyte viscosity.
The non-aqueous organic solvent may include a carbonate, an ester, an ether, or a ketone. Examples of carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Examples of esters include n-methyl acetate, n-ethyl acetate, n-propyl acetate, etc.
It is preferable to use a mixture of a chain carbonate and a cyclic carbonate. The cyclic carbonate and the chain carbonate are preferably mixed together in a volume ratio of 1:1 to 1:9. When the cyclic carbonate and the chain carbonate are mixed in the volume ratio of 1:1 to 1:9, and the mixture is used as an electrolyte, electrolyte performance may be enhanced.
In addition, the electrolyte of the present invention may further include mixtures of the carbonate solvents and aromatic hydrocarbon organic solvents. For the aromatic hydrocarbon organic solvent, a solvent represented by the following Formula 16 may be used. Examples of aromatic hydrocarbon solvents include benzene, fluorobenzene, toluene, trifluorotoluene, chlorobenzene, and xylene.
wherein, R¹¹ is a halogen or a C₁ to C₁₀ alkyl, and n is an integer of 0 to 6.
The carbonate solvents and the aromatic hydrocarbon solvents are preferably mixed together in a volume ratio of 1:1 to 30:1. When a carbonate solvent and an aromatic hydrocarbon solvent are mixed with each other in the aforementioned volume ratio, and the mixture is used as an electrolyte, electrolyte performance may be enhanced.
The present invention provides a lithium battery including the above electrolyte. For a positive active material, a compound being capable of intercalating/deintercalating lithium (a lithiated intercalation compound) reversibly is used. For the negative active material, a carbonaceous material being capable of intercalating/deintercalating lithium, a lithium metal, a lithium-containing alloy, and a carbonaceous material being capable of reversibly forming a lithium-containing compound by reacting lithium is used.
A lithium battery is prepared by the following process. A negative electrode and a positive electrode are fabricated by a conventional process, an insulating resin with a network structure is interposed between the negative and positive electrodes, and then the whole is wound or stacked to fabricate an electrode assembly. Then, the electrode assembly is inserted into a battery case, followed by sealing. The separator is a polyethylene or polypropylene monolayered separator, a polyethylene/polypropylene double layered separator, a polyethylene/polypropylene/polyethylene three layered separator, or a polypropylene/polyethylene/polypropylene three layered separator. A cross-sectional structure of the lithium battery prepared by the above process is shown in FIG. 1.
The lithium battery includes a non-rechargeable lithium battery or a rechargeable lithium battery.
The lithium battery including the electrolyte of the present invention has improved overcharge inhibiting properties over a battery including a conventional non-aqueous electrolyte.
The following examples further illustrate the present invention in detail, but are not to be construed to limit the scope thereof.

Comparative Example 1

94g of LiCoO₂ as a positive active material, 3g of Super P (acetylene black) as a conductive agent, and 3g of polyvinylidenefluoride (PVdF) as a binder were mixed in N-methyl-2-pyrrolidone (NMP) to prepare a positive slurry. The slurry was coated on an aluminum foil having a width of 4.9cm and a thickness of 147µm, dried, compressed, and then cut into a predetermined size, thus manufacturing a positive electrode.
90g of mesocarbon fiber (MCF from PETOCA Company) as a negative active material and 10g of PVdF as a binder were mixed to prepare a negative slurry. The slurry was coated on a copper foil having a width of 5.1cm and a thickness of 178µm, dried, and compressed, and then cut into a predetermined size, thus manufacturing a negative electrode.
Between the manufactured positive and negative electrodes, a polyethylene film separator was interposed followed by winding the whole to fabricate an electrode assembly. The manufactured electrode assembly was placed into a battery case and the electrolyte prepared as above was injected into the case under reduced pressure, thus completing the fabrication of the prismatic rechargeable lithium battery cell.
For an electrolyte, 1.3M LiPF₆ dissolved in a mixed solvent of ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, and fluorobenzene in a volume ratio of 30:55:5:10 was used.

Comparative Example 2

A prismatic rechargeable lithium battery was prepared according to the same method as in Comparative Example 1 except that 0.25g of a compound of the below Formula 17 for the additive was added to 5g of a solution including 1.3M LiPF₆ dissolved in a mixed solvent of ethylene carbonate, ethylmethyl carbonate, propylene carbonate and fluorobenzene in a volume ratio of 30:55:5:10 to prepare an electrolyte, and 2.3g of the electrolyte was added to the battery case.

Example 1

A prismatic rechargeable lithium battery was prepared according to the same method as in Comparative Example 1 except that 0.25g of 5-Fluoro-3H-benzofuran-2-one having the above Formula 6 for the additive was added to 5g of a solution including 1.3M LiPF₆ dissolved in a mixed solvent of ethylene carbonate, ethylmethyl carbonate, propylene carbonate and fluorobenzene in a volume ratio of 30:55:5:10 to prepare an electrolyte, and 2.3g of the electrolyte was added to the battery case.
Lithium battery cells of Example 1 and Comparative Examples 1 and 2 were overcharged at 2C to evaluate safety of the battery cells. Overcharge was performed by applying 2A of charge current to a fully discharged cell for 2.5 hours. Measurement results of safety of the cells according to Example 1 and Comparative Examples 1 and 2 are shown in Table 1. Table 1

Ignition

Comparative Example 1 ○

Comparative Example 2 ○

Example 1 ×
As shown in Table 1, the battery cells according to Example 1 have superb safety characteristics, compared with the cells according to Comparative Examples 1 and 2. The compound of the above Formula 17 has a high oxidation potential but induces ignition indicating bad safety characteristics.
A lithium battery including an electrolyte of the present invention shows improved overcharge characteristics over the battery including a conventional non-aqueous electrolyte.
While the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that various modifications and substitutions can be made thereto without departing from the spirit and scope of the present invention as set forth in the appended claims.

Claims

An electrolyte for a lithium battery, comprising:
a non-aqueous organic solvent;

a lithium salt; and

an additive having the following Formula 1:

wherein, X and Y are the same or different from each other and selected from O, S, CR₂, or NR, where here R is H, a halogen, or an alkyl having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and both X and Y are not oxygen (O),

R_a to R_d are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and

at least one of R_a to R_d is a halogen.
The electrolyte of claim 1, wherein the R is H, a halogen, or a C₁-C₈ alkyl.
The electrolyte of claim 1, wherein the halogen is fluorine.
The electrolyte of claim 1, wherein the additive is represented by the following Formula 2:
wherein, R¹ and R² are the same or different from each other and selected from H, a halogen, an alkyl having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle,
R³ to R⁶ are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R³ to R⁶ is a halogen.
The electrolyte of claim 1, wherein the additive is represented by the following Formula 3:
wherein, R_a to R_d are the same or different from each other and selected from a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R_a to R_d is a halogen.
The electrolyte of claim 1, wherein the additive is represented by the following Formula 4:
wherein, R¹ to R⁴ are the same or different from each other and selected from H, a halogen, an alkyl having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle,
R⁵ to R⁸ are the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R⁵ to R⁸ is a halogen.
The electrolyte of claim 1, wherein the additive is represented by the following Formula 5:
wherein, R_a to R_d is the same or different from each other and selected from H, a halogen, an alkoxy group having a carbon number of less than or equal to 8, or an unsaturated or saturated alkyl group having a carbon number of less than or equal to 8, or neighboring alkyl groups are combined to each other to form a cycle or hetero cycle, and
at least one of R_a to R_d is a halogen.
The electrolyte of claim 1, wherein the additive is represented by the following Formulas 6 to 15:
The electrolyte of claim 1, wherein an amount of the additive is 0.01 wt% to 50 wt% based on the total weight of electrolyte.
The electrolyte of claim 1, wherein the lithium salt is at least one selected from the group consisting of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃, Li(CF₃SO₂)₂N, LiC₄F₉SO₃, LiAlO₄, LiAlCl₄, LiN(C_xF_2x+1SO₂)(C_yF_2y+1SO₂) (where x and y are natural numbers), LiCl, and Lil.
The electrolyte of claim 1, wherein a concentration of the lithium salt is 0.6M to 2.0M.
The electrolyte of claim 1, wherein the non-aqueous organic solvent is at least one selected from the group consisting of a carbonate, an ester, an ether, and a ketone.
The electrolyte of claim 12, wherein the carbonates comprise at least one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).
The electrolyte of claim 12, wherein the carbonate is a mixture of a cyclic carbonate and a linear carbonate.
The electrolyte of claim 1, wherein the non-aqueous solvent is a mixture of a carbonate solvent and an aromatic hydrocarbon solvent.
The electrolyte of claim 15, wherein the aromatic hydrocarbon solvent is represented by the following Formula 16:
wherein R¹¹ is a halogen or a C₁ to C₁₀ alkyl, and n is an integer of 0 to 6.
The electrolyte of claim 15, wherein the aromatic hydrocarbon solvent comprises at least one selected from the group consisting of benzene, fluorobenzene, toluene, trifluorotoluene, chlorobenzene, and xylene.
The electrolyte of claim 15, wherein the carbonate solvent and the aromatic hydrocarbon solvent are mixed in a volume ratio of 1:1 to 30:1.
A lithium battery comprising:
an electrolyte according to claim 1;

a positive electrode including a positive active material being capable of intercalating and deintercalating lithium ions; and

a negative electrode including an active material selected from the group consisting of a material being capable of intercalating/deintercalating lithium ions, a lithium metal, a lithium-containing alloy, and a material being capable of forming a lithium-containing compound by reversibly reacting lithium.